Singlet oxygen generation on a superhydrophobic surface: Effect of photosensitizer coating and incident wavelength on 1O2 yields.

Photochemical generation of singlet oxygen (¹O₂) often relies on homogenous systems; however, a dissolved photosensitizer (PS) may be unsuitable for some applications because it is difficult to recover, expensive to replenish, and hazardous to the environment. Isolation of the PS onto a solid support can overcome these limitations, but implementation faces other challenges, including agglomeration of the solid PS, physical quenching of ¹O₂ by the support, photooxidation of the PS, and hypoxic environments. Here, we explore a superhydrophobic polydimethylsiloxane (SH-PDMS) support coated with the photosensitizer 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin (TFPP). This approach seeks to address the challenges of a heterogeneous system by using a support that exhibits low ¹O₂ physical quenching rates, a fluorinated PS that is chemically resistant to photooxidation, and a superhydrophobic surface that entraps a layer of air, thus preventing hypoxia. Absorbance and fluorescence spectroscopy reveal the monomeric arrangement of TFPP on SH-PDMS surfaces, a surprising but favorable characteristic for a solid-phase PS on ¹O₂ yields. We also investigated the effect of incident wavelength on ¹O₂ yields for TFPP in aqueous solution and immobilized on SH-PDMS and found overall yields to be dependent on the absorption coefficient, while the yield per absorbed photon exhibited wavelength independence, in accordance with Kasha-Vavilov's rule.